2 Introduction to Plastics
and Polymers
The most basic component of plastic and elas-
tomer materials is polymer. The word polymer is
derived from the Greek term for “many parts.”
Polymers are large molecules that comprised many
repeat units called monomers that have been chem-
ically bonded together into long chains. Since World
War II, the chemical industry has developed a large
number of synthetic polymers to satisfy the needs of
the materials for a diverse range of products,
including paints, coatings, fibers, films, elastomers,
and structural plastics. Literally, thousands of mate-
rials can be called “plastics,” although the term today
is typically reserved for polymeric materials,
excluding fibers, which can be molded or formed into
solids or semisolid objects. The subject of this
section includes polymerization chemistry and the
different types of polymers and how they can differ
from each other. Since plastics are rarely “neat,”
reinforcement, fillers and additives are reviewed. A
basic understanding of plastic and polymer chem-
istry will make the discussion of permeation of
specific plastics, films, and membranes easier to
understand, and it also provides a basis for the
introductions of the plastic families in later chapters.
This section is taken from The Effect of Temperature
and Other Factors on Plastics book, but it has been
rewritten, expanded, and refocused on permeation
properties.
2.1 Polymerization
Polymerization is the process of chemically
bonding monomer building blocks to form large
molecules. Commercial polymer molecules are
usually thousands of repeat units long. Polymeriza-
tion can proceed by one of the several methods. The
two most common methods are called addition and
condensation polymerization.
In addition polymerization, a chain reaction adds
new monomer units to the growing polymer
Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10002-5
Copyright Ó 2012 Elsevier Inc. All rights reserved.
molecule one at a time through double or triple bonds
in the monomer. Each new monomer unit creates an
active site for the next attachment. The net result is
shown in Fig. 2.1. Many of the plastics discussed in
a later chapter of this book are formed in this manner.
Some of the plastics made by addition polymeriza-
tion include polyethylene (PE), polyvinyl chloride
(PVC), acrylics, polystyrene, and polyoxymethylene
(acetal).
The other common method is condensation poly-
merization in which the reaction between monomer
units and the growing polymer chain end group
releases a small molecule, often water as shown in
Fig. 2.2. This reversible reaction will reach equilib-
rium and halt unless this small molecular by-product
is removed. Polyesters and polyamides are among
the plastics made by this process.
Understanding the polymerization process used to
make a particular plastic gives insight into the nature
of the plastic. For example, plastics made via
condensation polymerization, in which water is
released, can degrade when exposed to water at high
temperature. Polyesters such as polyethylene tere-
phthalate (PET) can degrade by a process called
hydrolysis when exposed to acidic, basic, or even
some neutral environments severing the polymer
chains. As a result, the properties of the polymer are
degraded.
2.2 Copolymers
A copolymer is a polymer formed when two (or
more) different types of monomer are linked in
Figure 2.1 Addition polymerization.
21
22 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

Figure 2.2 Condensation

polymerization.

the same polymer chain, as opposed to a homopol- A polymer that consists of large grouped blocks of
ymer where only one monomer is used. If exactly each of the monomers is also considered a block
three monomers are used, it is called a terpolymer. copolymer:
Monomers are only occasionally symmetric; the
molecular arrangement is the same no matter
which end of the monomer molecule you are
looking at. The arrangement of the monomers in
a copolymer can be head-to-tail, head-to-head, or When chains of a polymer made of monomer B
tail-to-tail. Since a copolymer consists of at least are connected onto a polymer chain of monomer A,
two types of repeating units, copolymers can be we have a graft copolymer:
classified based on how these units are arranged
along the chain. These classifications include the
following:

Alternating copolymer

Random copolymer (statistical copolymer)

Block copolymer

Graft copolymer.

When the two monomers are arranged in an alter-

nating fashion, the polymer is called, of course, an
alternating copolymer:

High-impact polystyrene (HIPS) is a graft copol-

In the following examples, A and B are different
monomers. Keep in mind that A and B do not have
to be present in a one-to-one ratio. In a random
copolymer, the two monomers may follow any
order:
ymer. It is a polystyrene backbone with chains of
polybutadiene grafted onto the backbone. The poly-
styrene gives the material strength, but the rubbery
polybutadiene chains give it resilience to make it less
brittle.

2.3 Linear, Branched, and

Cross-Linked Polymers
Some polymers are linear, a long chain of con-
In a block copolymer, all of one type of monomers
nected monomers. PE, PVC, Nylon 66, and poly-
are grouped together, and all of the second mono-
methyl methacrylate are some linear commercial
mers are grouped together. A block copolymer can
examples found in this book. Branched polymers can
be thought of as two homopolymers joined together
be visualized as a linear polymer with side chains of
at the ends:
the same polymer attached to the main chain. While
the branches may in turn be branched, they do not
connect to another polymer chain. The ends of the
branches are not connected to anything. Special
2: I NTRODUCTION TO P LASTICS AND P OLYMERS 23

electronegativity of common atoms in the polymers

is given as follows:

F > O > Cl and N > Br > C and H:

Figure 2.3 Linear, branched, and cross-linked
polymers.
types of branched polymers include star polymers,
comb polymers, brush polymers, dendronized poly-
mers,1 ladders, and dendrimers. Cross-linked poly-
mer, sometimes called network polymer, is one in
which different chains are connected. Essentially, the
branches are connected to different polymer chains
on the ends. These three polymer structures are
shown in Fig. 2.3.
2.4 Polarity
A molecule is two or more atoms joined by
a covalent bond. Basically, the positively charged
atom nuclei share the negatively charged electrons.
However, if the atoms are different, they may not
share the electrons equally. The electrons will be
denser around one of the atoms. This would make
that end more negatively charged than the other
end and that creates a negative pole and a positive
pole (a dipole), and such a bond is said to be
a polar bond and the molecule is polar and has
a dipole moment. A measure of how much an
atom attracts electrons is electronegativity. The
The polarity of a molecule affects the attraction
between molecular chains, which affects the struc-
ture of the polymer and the attraction of polar
molecules, so one would expect polarity to affect
solubility which in turn affects permeability.
How does one predict molecular polarity? When
there are no polar bonds in a molecule, there is no
permanent charge difference between one part of the
molecule and another, so the molecule is nonpolar. For
example, the Cl2 molecule has no polar bonds because
the electron charge is identical on both atoms. It is
therefore a nonpolar molecule. The CeC and CeH
bonds in hydrocarbon molecules, such as ethane,
C2H6, are not significantly polar, hence hydrocarbons
are nonpolar molecular substances and hydrocarbon
polymers like PE or polypropylene are also nonpolar.
However, a molecule can possess polar bonds and
still be nonpolar. If the polar bonds are evenly (or
symmetrically) distributed, the bond dipoles cancel
and do not create a molecular dipole. For example, the
three bonds in a molecule of CCl4 are significantly
polar, but they are symmetrically arranged around the
central carbon atom. No side of the molecule has
more negative or positive charge than another side,
and hence the molecule is nonpolar (Table 2.1).
Generally, polar polymers are more permeable to
water than nonpolar polymers. Figure 2.4 shows
a qualitative ranking of some polymer polarities.
2.5 Unsaturation
Up to this point in the discussion of polymer
chemistry, the atom-to-atom structure has not been
discussed. The covalent bonds between atoms in

Table 2.1 Dipole Moments in Some Small Molecules

Dipole Dipole Dipole

Molecule Moment Molecule Moment Molecule Moment
H2 0 HF 1.75 CH4 0.0
O2 0 H2O 1.84 CH3Cl 1.86
N2 0 NH3 1.46 CCl4 0
Cl2 0 NF3 0.24 CO2 0
Br2 0 BF3 0
24 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

High Polarity Nylon 6/6 Examples:

Nylon 6 Ethylene: C2H4
Polyethylene terephthalate (PET)
Cellulose Acetate
NBR (50% acrylonitrile) 2C þ 2 þ N  X  H
Polyurethane DoU ¼
Nitrocellulose
2
Epoxy 22þ2þ004
Polycarbonate (PC) ¼ ¼ 1 (2)
2
Polymethyl methacrylate (PMMA)
Polyvinyl acetate
NBR (30% acrylonitrile) Benzene: C6H6
Acrylate elastomers
Polyvinyl butyral
Polyepichlorohydrin
2C þ 2 þ N  X  H
Cellulose acetate butyrate DoU ¼
Polystyrene 2
Polyvinyl alcohol 26þ2þ006
Polychloroprene ¼ ¼ 4 (3)
Polyethylene 2
NBR (20% acrylonitrile)
Chlorinated polyethylene
SBR When polymers are used the formula shown is often
Polybutadiene the repeating unit. This will often have two bonds that
Natural Rubber are shown to which the repeating unit is supposed to
Halogenated Butyl
Polypropylene attach. When applying a DoU formula to the repeating
EPDM unit, one would remove the “þ2” from it.
Butyl Rubber
Perfluorinated polymers
Examples:
Low Polarity PE: e(CH2eCH2)ne

Figure 2.4 Qualitative ranking of polymer polarities. 2C þ N  X  H

DoU ¼
2 (4)
22þ004
a polymer can be single, double, triple bonds, or even ¼ ¼ 0
rings. The presence of bonds other than single bonds 2
generally makes the polymer molecule stiffer and
reduces rotation along the polymer chain, and this Polyphenylene sulfone (PPS): e(C6H4eS)ne
can affect its properties. It is easier to discuss
molecules first and then extend that discussion to 2C þ N  X  H
DoU ¼
polymers. Saturated molecules only contain single 2
(5)
bonds with no rings. 26þ004
Often when talking about molecular unsaturation, ¼ ¼ 4
2
the degree of unsaturation (DoU) is noted. The DoU
can be calculated from the below equation if the
molecular formula is given. 2.6 Steric Hindrance
2C þ 2 þ N  X  H As described earlier in this chapter, polymers are
DoU ¼ ; (1)
2 long chains of atoms linked together. They may be
flexible and bendable. To explain this, one may
where visualize them as a ball-and-stick model. In
C is the number of carbons chemistry, the ball-and-stick model is a molecular
N is the number of nitrogens model of a chemical substance, which aims to
X is the number of halogens (F, Cl, Br, I) display both the 3D position of the atoms and the
H is the number of hydrogens. bonds between them. The atoms are typically rep-
resented by spheres, connected by rods that repre-
Oxygen and sulfur are not included in the formula sent the bonds. Double and triple bonds are usually
because saturation is unaffected by these elements. represented by two and three curved rods,
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
Figure 2.5 Steric hindrance shown with a ball-and-
stick molecular model.
respectively. The chemical element of each atom is
often indicated by the sphere’s color. The top of
Fig. 2.5 shows a drawing of a ball-and-stick model
of a molecule. Figure 2.5 also indicates that there is
free rotation around the single bonds. If there was
a double or triple bond, there would not be any
rotation possible around those bonds. Similarly,
ring structures, while they might flex a little bit,
inhibit rotation. In some cases, such as shown in
the bottom of Fig. 2.5, large atoms or bulky side
groups might bump into each other as the molecule
rotates around single bonds. This is called sterically
hindered or steric hindrance. Hindered or inhibited
rotation stiffens the polymer molecule and
dramatically affects its physical properties.
2.7 Isomers
Isomers (from Greek isomerès; isos ¼ “equal” and
méros ¼ “part”) are compounds with the same
molecular formula but a different arrangement of the
atoms in space. There are many kinds of isomers, and
the properties can differ widely or almost not at all.
2.7.1 Structural Isomers
Structural isomers have the atoms that are
arranged in a completely different order as shown in
Fig. 2.6. Here, both polymer repeating groups have
the same formula, eC4H8e, but the atoms are
25
Figure 2.6 Structural isomers.
Figure 2.7 Head-to-tail isomers.2
arranged differently. The properties of structural
isomers may be very different from each other.
Often the repeating group in a polymer has exactly
the same formula, but the repeating group is flipped
over as shown in Fig. 2.7. If one views the repeating
group as having a head and a tail, then the different
ways to connect neighboring repeating units are
headetail, headehead, and tailetail.
2.7.2 Geometric Isomers
When there is a carbonecarbon double bond in
a molecule, there might also be two ways to arrange
the groups attached to the double bonds. This is best
seen in side-by-side structures such as shown in
Fig. 2.8.
These are called geometric isomers that owe
their existence to hindered rotation about double
bonds. If the substituents are on the same side of
the double bond then the isomer is referred to as
cis (Latin: on this side). If the substituents are on
Figure 2.8 The cis and trans isomers.
26
the opposite side of the double bond then it is
referred to as trans (Latin: across).
2.7.3 Stereoisomersd
Syndiotactic, Isotactic,
and Atactic
Stereoisomerism occurs when two or more mole-
cules have identical molecular formula and the same
structural formula (i.e., the atoms are arranged in the
same order). However, they differ in their 2D or 3D
spatial arrangements of their bonds, which mean
different spatial arrangement of the atoms, even
though they are bonded in the same order. This may
best be understood by an example.
Polypropylenes all have the same simplified
structural polymer formula of polypropene as shown
in Fig. 2.9.
However, there are subtle differences in the ways
to draw this structure. Figure 2.10 shows a longer
Figure 2.9 The structure of polypropene.
Figure 2.10 The structure of atactic polypropene.
Figure 2.11 The structure of isotactic polypropene.
Figure 2.12 The structure of syndiotactic polypropene.
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
structure of polypropene and some 3D structures.
This structure shows how some bonds (the dotted
lines) are behind the plane of the paper and others
stick out of the paper (the ones on the ends of the
little triangular wedges). In this structure, some of
the CH3 groups are above the paper plane and others
are behind the paper plane. This is called atactic
polypropene.
Atactic polypropene has at random about 50% of
hydrogen/methyl groups in front/back of CeCeC
chain viewing plane. This form of polypropene is
amorphous (noncrystalline, discussed in Section
2.9.3) and has an irregular structure due to the
random arrangement of the methyl groups attached
to the main carbonecarbon chain. It tends to be
softer and more flexible than the other forms
(described below) and is used for roofing materials,
sealants, and other weatherproof coatings.
Isotactic polypropene has all of the methyl groups
in front of CeCeC chain viewing plane and all of the
H’s at back as shown in Fig. 2.11. This stereoregular
structure maximizes the moleculeemolecule contact
and so increases the intermolecular forces compared
with the atactic form. This regular structure is much
stronger (than the atactic form above) and is used in
sheet and film form for packaging and carpet fibers.
Syndiotactic polypropene has a regular alternation
of 50% of hydrogen/methyl groups in front/back
of CeCeC chain viewing plane as shown in Fig. 2.12.
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
Its properties are similar to isotactic polypropene
rather than the atactic form, that is, the regular polymer
structure produces stronger intermolecular forces and
a more crystalline form than the atactic polypropene.
2.8 Inter- and Intramolecular
Attractions in Polymers
The attractive forces between different polymer
chains or segments within polymer chains play
a large part in determining a polymer’s properties. As
mentioned in Section 2.4, atoms can have polarity or
dipole moments. Since negative charges are attracted
to the opposite positive charges and repelled by like
charges, it is possible to generate attractions that lead
to certain structures.
2.8.1 Hydrogen Bonding
One of the strongest dipole interactions is the
attraction of some oxygen atoms to hydrogen atoms,
even though they are covalently bonded to other
atoms. This is called hydrogen bonding, and a sche-
matic representation is shown in Fig. 2.13. The NeH
bond provides a dipole when the hydrogen has
a slightly positive charge and the nitrogen has a slight
negative charge. The carbonyl group, the C¼O,
likewise is a dipole, where the oxygen has the slight
negative charge and the carbon is slightly positive.
When polymer chains line up, these hydrogen bonds
are formed (indicated by the wide gray bars in the
figure), bonds that are far weaker than the covalent
bonds but bonds of significant strength nonetheless.
Other side groups on the chain polymer can lend
the polymer to hydrogen bonding between its own
27
chains. These stronger forces typically result in
higher tensile strength and higher crystalline melting
points. Polyesters have dipoleedipole bonding
between the oxygen atoms in C¼O groups and the
hydrogen atoms in HeC groups. Dipole bonding is
not as strong as hydrogen bonding.
2.8.2 Van der Waals Forces
Many polymers, such as polyethylene, have no
permanent dipole. However, attractive forces
between polyethylene chains arise from weak forces
called Van der Waals forces. Van der Waals forces
are much weaker than chemical bonds, and random
thermal motion around room temperature can usually
overcome or disrupt them.
Molecules can be thought of as being surrounded
by a cloud of negative electrons. But the electrons are
mobile, and at any one instant, they might find
themselves toward one end of the molecule, making
that end slightly negative (d). The other end will be
momentarily short of electrons and so becomes (dþ).
Basically, temporary fluctuating dipoles are present in
all molecules, and the forces due to these dipoles are
the basis for Van der Waals attraction. Van der Waals
forces are quite weak, however, so polyethylene can
have a lower melting temperature compared to other
polymers that have hydrogen bonding.
2.8.3 Chain Entanglement
Polymer molecules are long chains, which can
become entangled with one another, much like a bowl
of spaghetti. Along with intermolecular forces, chain
entanglement is an important factor contributing to
the physical properties of polymers. The difficulty in
Figure 2.13 Schematic
representation of hydrogen
bonding in a pair of polymer
chains.
28 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

untangling their chains makes polymers and the

plastic made from them strong and resilient.

2.9 General Classifications

Besides the chemical structures of the polymers in
the plastics, there are several other characterizations
that are important including molecular weight,
thermoplastics vs. thermosets, and crystallinity.

2.9.1 Molecular Weight

The molecular weight of a polymer is the sum of
the atomic weights of individual atoms that comprise
a molecule. It indicates the average length of the
bulk resin’s polymer chains. All polymer molecules
of a particular grade do not have the exact same
molecular weight. There is a range or distribution of
molecular weights. There are two important but
different ways to calculate molecular weight. The
most important one is called the number average
molecular weight, Mn. For all “i” molecules in
a sample, the number average molecular weight is
calculated using Eqn (6):
P
Ni Mi
Mn ¼ iP ; (6)
Ni
i
where
i is the number of polymer molecules
Ni is the number of molecules that have the
molecular weight Mi.
The weight average molecular weight is a different
calculation as in Eqn (7)
P different molecular weight grades. These resins can
Ni Mi2
Mw ¼ P
i
(7)
Ni Mi
i
Figure 2.14 shows a molecular weight distribu-
tion chart with the two different molecular weight
measures noted on it. The ratio Mw/Mn is called the
molar-mass dispersity index3 [often called poly-
dispersity (PDI)].3 If all the polymer chains are
exactly the same, then the number average and
weight average molecular weights are exactly the
same, and the PDI is “1.” The larger the molar-mass
dispersity index, the wider the molecular weight
distribution. The molecular weight range can affect
many properties of plastic materials.
Figure 2.14 Hypothetical molecular weight distribu-
tion plot showing number and weight average molec-
ular weights.
Another common means of expressing the length of
a polymer chain is the degree of polymerization, this
quantifies the average number of monomers incor-
porated into the polymer chain. The average molec-
ular weight can be determined by several means, but
this subject is beyond the scope of this book. Low-
molecular-weight polyethylene chains have back-
bones as small as 1000 carbon atoms long. Ultrahigh-
molecular-weight polyethylene chains can have
500,000 carbon atoms along their length. Many
plastics are available in a variety of chain lengths or
also be classified indirectly by a viscosity value, rather
than molecular weight. Within a resin family, such as
polycarbonate, high-molecular-weight grades have
higher melt viscosities. For example, in the viscosity
test for polycarbonate, the melt flow rate ranges from
approximately 4 g/10 min for the highest molecular
weight, standard grades, to more than 60 g/10 min for
lowest molecular weight, high flow, specialty grades.
Selecting the correct molecular weight for an
injection molding application generally involves
a balance between filling ease and material perfor-
mance. If the application has thin-walled sections,
a lower molecular-weight/lower viscosity grade
offers better flow. For normal wall thicknesses, these
resins also offer faster mold cycle times and fewer
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
molded in stresses. The stiffer flowing, high-molec-
ular-weight resins offer the ultimate material
performance, being tougher and more resistant to
chemical and environmental attack. High-molecular-
weight films orient better (see Section 3.8 for
details). Low-molecular-weight films are often opti-
cally clearer.
Molecular weight of the polymers that are used in
engineering plastics affects many of the plastics
properties. Although it is not always known exactly
what the molecular weights are, as mentioned above
higher flowing plastics of a given series of products
generally are low-molecular-weight polymers.
Molecular weight can affect the permeation proper-
ties as shown in Fig. 2.15.
Dispersity can also have an effect on permeation
rates. For polymers, large molar-mass dispersity
index implies that a significant amount of low-
molecular-weight polymer is present and that can act
like a plasticizer, which increases permeation rates
(see Section 2.10.3.10).
2.9.2 Thermosets vs.
Thermoplastics
A plastic falls into one of two broad categories
depending on its response to heat: thermoplastics or
thermosets. Thermoplastics soften and melt when
Figure 2.15 Water permeation of ethyleneevinyl
alcohol copolymer vs. polymer molecular weight.4
29
heated and harden when cooled. Because of this
behavior, these resins can be injection molded,
extruded, or formed via other molding techniques.
This behavior also allows production scrap runners
and trimmings to be reground and reused. Thermo-
plastics can often be recycled.
Unlike thermoplastics, thermosets react chemically
to form cross-links, as described earlier, that limit
chain movement. This network of polymer chains
tends to degrade, rather than soften, when exposed to
excessive heat. Until recently, thermosets could not
be remelted and reused after initial curing. Recent
advances in recycling have provided new methods for
remelting and reusing thermoset materials.
2.9.3 Crystalline vs. Amorphous
Thermoplastics are further classified by their
crystallinity or the degree of order within the overall
structure of the polymer. As a crystalline resin cools
from the melt, polymer chains fold or align into
highly ordered crystalline structures as shown in
Fig. 2.16.
Some plastics can be completely amorphous or
crystalline. Often specifications in plastics will
report what percent of it is crystalline, such as 73%
crystallinity. Generally, polymer chains with bulky
side groups cannot form crystalline regions. The
degree of crystallinity depends on both the polymer
and the processing technique. Some polymers such
as polyethylene crystallize quickly and reach high
levels of crystallinity. Others, such as PET poly-
ester, require slow cooling to crystallize. If cooled
Figure 2.16 Many plastics have crystalline and
amorphous regions.
30
quickly, PET polyester remains amorphous in the
final product.
Crystalline and amorphous plastics have several
characteristic differences. Amorphous polymers do
not have a sharp melting point, but do have what is
called a glass transition temperature, Tg. A glass-
transition temperature is the temperature at which
a polymer changes from hard and brittle to soft and
pliable. The force to generate flow in amorphous
materials diminishes slowly as the temperature rises
above the glass transition temperature. In crystalline
resins, the force requirements diminish quickly as the
material is heated above its crystalline melt temper-
ature. Because of these easier flow characteristics,
crystalline resins have an advantage in filling thin-
walled sections of a mold. Crystalline resins gener-
ally have superior chemical resistance, greater
stability at elevated temperatures, and better creep
resistance. Amorphous plastics typically have better
impact strength, less mold shrinkage, and less final
part warping than crystalline materials. Higher
crystallinity usually leads to lower permeation rates.
End-use requirements usually dictate whether an
amorphous or crystalline resin is preferred.
2.9.4 Orientation
When films are made from plastic polymers, the
polymer molecules are randomly intertwined like a
bowl of spaghetti. They are amorphous. They are
coiled and twisted and have no particular alignment,
unless they are crystallized during cooling or aging.
However, if the film is drawn or stretched, the
amorphous regions of the polymer chains are
straightened and aligned to the direction of drawing.
The process for doing this is discussed later in this
chapter. Oriented films usually have lower oxygen
and water permeation rates.
2.10 Plastic Compositions
Plastics are usually formulated products meaning
that they are not always neat polymers. They may be
blends of polymers and may have any or many
additives used to tailor performance properties.
2.10.1 Polymer Blends
Polymers can often be blended. Occasionally,
blended polymers have properties that exceed those
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
of either of the constituents. For instance, blends of
polycarbonate resin and PET polyester, originally
created to improve the chemical resistance of poly-
carbonate, actually have fatigue resistance and low-
temperature impact resistance superior to either of
the individual polymers.
Sometimes, a material is needed that has some of
the properties of one polymer and some of the
properties of another polymer. Instead of going back
to the laboratory and trying to synthesize a brand new
polymer with all the properties wanted, two poly-
mers can be melted together to form a blend, which
will hopefully have some properties of both.
Two polymers that do actually mix well are poly-
styrene and polyphenylene oxide. A few other exam-
ples of polymer pairs that will blend are as follows:

PET with polybutylene terephthalate

Polymethyl methacrylate with polyvinylidene
fluoride
Phase-separated mixtures are obtained when one
tries to mix most polymers. But strangely enough,
the phase-separated materials often turn out to be
rather useful. They are called immiscible blends.
Polystyrene and polybutadiene are immiscible.
When polystyrene is mixed with a small amount of
polybutadiene, the two polymers do not blend. The
polybutadiene separates from the polystyrene into
little spherical blobs. If this mixture is viewed under
a high-power microscope, something that looks like
the picture in Fig. 2.17 would be seen.
Multiphase polymer blends are of major economic
importance in the polymer industry. The most
Figure 2.17 Immiscible blend of polystyrene and
polybutadiene.
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
common examples involve the impact modification
of a thermoplastic by the microdispersion of a rubber
into a brittle polymer matrix. Most commercial
blends consist of two polymers combined with small
amounts of a third, compatibilizing polymer, typi-
cally a block or graft copolymer.
Multiphase polymer blends can be easier to
process than a single polymer with similar proper-
ties. The possible blends from a given set of poly-
mers offer many more physical properties than do the
individual polymers. This approach has shown some
success but becomes cumbersome when more than
a few components are involved.
Blending two or more polymers offers yet another
method of tailoring resins to a specific application.
Because blends are only physical mixtures, the
resulting polymer usually has physical and
mechanical properties that lie somewhere between
the values of its constituent materials. For instance,
an automotive bumper made from a blend of poly-
carbonate resin and thermoplastic polyurethane
elastomer gains rigidity from the polycarbonate resin
and retains most of the flexibility and paintability of
the polyurethane elastomer. For business machine
housings, a blend of polycarbonate and acrylonitrile-
butadiene-styrene copolymer (ABS) resins offers the
enhanced performance of polycarbonate flame
retardance and ultraviolet (UV) stability at a lower
cost.
Additional information on the subject of polymer
blends is available in the literature.5e7
2.10.2 Elastomers
Elastomers are a class of polymeric materials that
can be repeatedly stretched to over twice the original
length with little or no permanent deformation.
Elastomers can be made of either thermoplastic or
thermoset materials and are generally tested and
categorized differently than rigid materials. They are
commonly selected according to their hardness and
energy absorption characteristics, properties rarely
considered in rigid thermoplastics. Elastomers are
found in numerous applications, such as automotive
bumpers and industrial hoses.
2.10.3 Additives
The properties of neat polymers are often not ideal
for production or the end use. When this is the case,
materials are added to the polymer to improve the
31
performance shortfall. The additives can improve the
processing and performance of the plastic. For
whatever reason the additive is used, it can affect the
permeation, diffusion, and solubility properties.
Additives encompass a wide range of substances
that aid processing or add value to the final
product.8,9 Found in virtually all plastics, most
additives are incorporated into a resin family by the
supplier as part of a proprietary package. For
example, you can choose standard polycarbonate
resin grades with additives for improved internal
mold release, UV stabilization, and flame retardance;
or you can choose nylon grades with additives to
improve impact performance.
Additives often determine the success or failure of
a resin or system in a particular application. Many
common additives are discussed in the following
sections. Except for reinforcement fillers, most
additives are added in very small amounts.
2.10.3.1 Fillers, Reinforcement, and
Composites
Reinforcing fillers can be added in large amounts.
Some plastics may contain as much as 60% of
reinforcing fillers. Often, fibrous materials, such as
glass or carbon fibers, are added to resins to create
reinforced grades with enhanced properties. For
example, adding 30% of short glass fibers by weight
to nylon 6 improves creep resistance and increases
stiffness by 300%. These glass-reinforced plastics
usually suffer some loss of impact strength and
ultimate elongation, and these are more prone to
warping because of the relatively large difference in
mold shrinkage between the flow and cross-flow
directions.
Plastics with nonfibrous fillers such as glass
spheres or mineral powders generally exhibit higher
stiffness characteristics than unfilled resins, but not
as high as fiber-reinforced grades. Resins with
particulate fillers are less likely to warp and show
a decrease in mold shrinkage. Particulate fillers
typically reduce shrinkage by a percentage roughly
equal to the volume percentage of filler in the poly-
mer, an advantage in tight tolerance molding.
Often reinforced plastics are called composites.
Often, the plastic material containing the reinforce-
ment is referred to as the matrix. One can envision
a number of ways in which different reinforcing
materials might be arranged in a composite. Many of
these arrangements are shown in Fig. 2.18.
32
Figure 2.18 Several types of composite
materials.
While barrier films and membranes usually do use
fiber-reinforcing fillers, platelet and particulate
composites are used and laminate composites are
very common.
Particulates, in the form of pigments, to impart
color may be added. On occasion, particulate,
called extender, is added to reduce the amount of
relatively expensive polymer used, which reduces
overall cost.
Platelet additives may impart color and luster,
metallic appearance, or a pearlescent effect, but they
also can strongly affect permeation properties. Most
of these additives have little or no permeation
through themselves so when a film contains partic-
ulate additives, the permeating molecule must
follow a path around the particulate additive as
shown in Fig. 2.19. This is often called a tortuous
path effect.
Barrier enhancement due to tortuous path through
a platelet-filled film may be modeled by Eqn (8).10:
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
Vp
P c ¼ P0 (8)
1 þ ðVf Af Þ=2
where
P0 is the permeability coefficient of the neat
polymer
Vp is the volume fraction of polymer
Vf is the volume fraction of the flake filler
Af is the aspect ratio of the flake filler, length/
thickness (L/W in Fig. 2.19).
These variables assume that the particles are
completely separated (exfoliated) and planar in the
film. This is relatively easy to do in cast films and
coatings, a little less so in extruded and blown films,
much more difficult in molded items. Figure 2.20
shows graphically the effect that aspect ratio and
concentration of platelet fillers have on the inherent
permeability of the polymer matrix.
It has also been modeled for other shaped
particulate fillers including rods or cylinders and
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
Figure 2.20 Relative permeability vs. volume frac-
tion of platelet fillers of different aspect ratios.
spheres.11 Figure 2.21 shows the relative effective-
ness of particulate in various shapes on the perme-
ation coefficients vs. volume fraction of the
particulate.
2.10.3.2 Combustion Modifiers, Fire,
Flame Retardants, and Smoke
Suppressants
Combustion modifiers are added to polymers to
help retard the resulting parts from burning. Gener-
ally required for electrical and medical housing
applications, combustion modifiers and their
33
Figure 2.19 Tortuous path of
permeant molecule through
a particulate containing film.
Figure 2.21 Calculated change in the permeation of
a film containing particulate of a specified shape vs.
the amount of that particulate in the film.
amounts vary with the inherent flammability of the
base polymer. Polymers designed for these applica-
tions often are rated using an Underwriters Labora-
tories rating system. Use these ratings for
comparison purposes only, as they may not accu-
rately represent the hazard present under actual fire
conditions.
2.10.3.3 Release Agents
External release agents are lubricants, liquids, or
powders, which coat a mold cavity to facilitate part
removal. Internal release agents can accomplish the
34
same purpose. The identity of the release agent is
rarely disclosed, but frequently they are fine fluo-
ropolymer powders, called micropowders, silicone
resins, or waxes.
2.10.3.4 Slip Additives/Internal
Lubricants
When polymeric films slide over each other, there
is a resistance that is quantified in terms of the
coefficient of friction (COF). Films with high COF
tend to stick together instead of sliding over one
another. Sticking makes the handling, use, and
conversion of films difficult. To overcome sticking,
slip agents are added to the films.
Slip additives can be divided into two types:
migrating and nonmigrating types. Migrating slip
additives are the most common class, and they are
used above their solubility limit in the polymer.
These types of additives are molecules that have
two distinct parts, typically pictured as a head and
tail as shown in Fig. 2.22. One part of the molecule,
usually the head, is designed to be soluble in the
polymer (particularly when it is molten during
processing) making up the plastic. The other part,
the tail, is insoluble. As the plastic cools and
solidifies from its molten state, these molecules
migrate to the surface, where the insoluble end
“sticks up” reducing the COF. This process is shown
in Fig. 2.22. These additives are typically fatty acid
amides.
There are migrating slip additives that are not of
this two-part structure. One additive is per-
fluoropolyether (PFPE) synthetic oil marketed by
DuPontÔ under the trademark FluoroguardÒ , which
is an internal lubricant that imparts improved wear
and low-friction properties. Silicone fluids, such as
those made by Dow Corning, can also act as
Figure 2.22 Mode of action of
a typical migrating slip additive.
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
a boundary lubricant. Both these materials may
migrate to the surface of the plastic over time.
Some common nonmigrating slip additives
include the following:

Polytetrafluoroethylene (PTFE) in micropowder
form imparts the lowest COF of any internal lubri-
cant. Manufacturers and suppliers are many
including DuPontÔ ZonylÒ and 3M DyneonÔ.

Molybdenum disulfide, commonly called “moly,”
is a solid lubricant often used in bearing
applications.

Graphite is a solid lubricant used like molyb-
denum disulfide.
2.10.3.5 Antiblock Additives
Blocking is a surface effect between adjacent film
layers that stick to one another. Blocking is quanti-
fied by the force needed to separate two film layers
under controlled conditions. Two situations where
blocking is an issue are the opening of blown film
tubes after extrusion and film layer separation after
packing and storage. Antiblock additives are used to
overcome these issues.
Antiblock additives can be divided into two
classes: inorganic and organic. Chemically inert,
inorganic antiblock additives migrate to the film
surface and partially stick out of the surface to create
a microroughness of the film surface. Figure 2.23
illustrates this principle.
The detailed mechanism of how organic antiblock
additives work is not yet understood. It is thought
that a barrier layer is formed on the plastic film
surface, thus inhibiting the two adjacent plastic film
layers’ adhesion. Their usage is limited. Organic
antiblock additives were partially discussed above
and will not be further mentioned here.
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
Figure 2.23 Antiblock additives maintain film
separation.
2.10.3.6 Catalysts
Catalysts, substances that initiate or change the
rate of a chemical reaction, do not undergo
a permanent change in composition or become a part
of the molecular structure of the final product.
Occasionally used to describe a setting agent, hard-
ener, curing agent, promoter, etc., catalysts are added
in minute quantities, typically <1%.
2.10.3.7 Impact Modifiers and
Tougheners
Many plastics do not have sufficient impact
resistance for the use for which they are intended.
Rather than change to a different type of plastic,
they can be impact modified in order to fulfill the
performance in use requirements. Addition of
modifiers called impact modifiers or tougheners
can significantly improve impact resistance. This is
one of the most important additives. There are
many suppliers and chemical types of these
modifiers.
General purpose impact modification is a very low
level of impact modification. It improves room
temperature impact strength but does not take into
account any requirements for low-temperature
(<0  C) impact strength. For most of these types of
applications, only low levels of impact modifier will
be required (<10%).
Low-temperature impact strength is required for
applications that require a certain level of low-
temperature flexibility and resistance to break. This
35
is for example the case for many applications in the
appliance area. For this purpose, modifier levels
between 5% and 15% of mostly reactive modifiers
will be necessary. Reactive modifiers can chemically
bond to the base polymer.
Super tough impact strength may be required for
applications that should not lead to a failure of the part
even if hit at low temperatures (30 to 40  C) under
high speed. This requirement can only be fulfilled
with high levels (20e25%) of reactive impact modi-
fier with low glass transition temperature.
2.10.3.8 UV Stabilizers
Another way plastics may degrade is by exposure
to UV light. UV can initiate oxidation. Plastics that
are used outdoors or exposed to lamps emitting UV
radiation are subject to photooxidative degradation.
UV stabilizers are used to prevent and retard
photooxidation. Pigments and dyes may also be used
in applications not requiring transparency. Photoox-
idative degradation starts at the exposed surface and
propagates throughout the material.
2.10.3.9 Optical Brighteners
Many polymers have a slight yellowish color.
They can be modified to appear whiter and brighter
by increasing reflected bluish light (in the range of
400e600 nm). One way to accomplish this is by
using an additive that absorbs in the UV range but
reemits the energy at higher wavelength. This effect
is called fluorescence, and these types of additives
are called optical brighteners or fluorescent whit-
ening agents.
2.10.3.10 Plasticizers
Plasticizers are added to help maintain flexibility
in a plastic. Various phthalates are commonly used
for this purpose. Since they are small molecules, they
may extract or leach out of the plastic causing a loss
of flexibility with time. Just as deliberately added,
small molecules may leach out, small molecules
from the environment may be absorbed by the plastic
and act like a plasticizer. The absorption of water by
nylons (polyamides) is an example.
Plasticizers increase the space between the poly-
mers chains and so they are expected to increase the
permeability as well. This is shown in Fig. 2.24,
which shows the effect of plasticizer level on the
permeability of cellulose acetate films.
36
Figure 2.24 Effect of plasticizer content on the
permeability of hydrogen and carbon dioxide through
cellulose acetate at different temperatures.12
2.10.3.11 Pigments, Extenders, Dyes,
and Mica
Pigments are added to give a color to the plastic,
but they may also affect the physical properties.
Extenders are usually cheap materials added to
reduce the cost of plastic resins. Dyes are colorants
that are chemically different from pigments. Mica is
a special pigment added to impact sparkle or metallic
appearance.
2.10.3.12 Coupling Agents
The purpose of adding fillers is either to lower the
cost of the polymer, make it tougher or stiffer, or make
it flame retardant, so that it does not burn when it is
ignited. Often the addition of the filler will reduce the
elongation at break, the flexibility, and in many cases
the toughness of the polymer because the fillers are
added at very high levels. One reason for the degra-
dation of properties is that the fillers in most cases are
not compatible with the polymers. The addition of
coupling agents can improve the compatibility of the
filler with the polymer. As a result, the polymer will
like the filler more, the filler will adhere better to the
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
polymer matrix, and the properties of the final mixture
(e.g., elongation and flexibility) will be enhanced.
2.10.3.13 Thermal Stabilizers
One of the limiting factors in the use of plastics at
high temperatures is their tendency to not only
become softer but also to thermally degrade.
Thermal degradation can present an upper limit to
the service temperature of plastics. Thermal degra-
dation can occur at temperatures much lower than
those at which mechanical failure is likely to occur.
Plastics can be protected from thermal degradation
by incorporating stabilizers into them. Stabilizers
can work in a variety of ways but discussion of these
mechanisms is beyond the purpose of this book.
2.10.3.14 Antistats
Antistatic additives are capable of modifying
properties of plastics in such a way that they become
antistatic, conductive, and/or improve electromag-
netic interference (EMI) shielding. Carbon fibers,
conductive carbon powders, and other electrically
conductive materials are used for this purpose.
When two (organic) substrates rub against each
other, electrostatic charges can build up. This is
known as tribocharging. Electrostatic charges can
impact plastic parts in several ways; one of the most
annoying being the attraction of dust particles. One
way to counter this effect is to use antistats (or
antistatic additives). This is principally a surface
effect, although one potential counter measure
(conductive fillers) converts it into a bulk effect.
Tools that decrease electrostatic charges and hence
increase the conductivity of an organic substrate can
be classified as follows:

external antistat (surface effect)

conductive filler (bulk and surface effect)

internal antistat (surface effect)
An external antistat is applied via a carrier medium to
the surface of the plastic part. The
same considerations and limitations apply as with
nonmigrating slip additives. Conductive filler is
incorporated into the organic substrates and builds up
a conductive network on a molecular level. Although
both approaches are used in organic substrates, they
are not the most common.
An internal antistat is compounded into the
organic substrate and migrates to the plastic part
2: I NTRODUCTION TO P LASTICS AND P OLYMERS
surface. The same principle considerations apply as
for migrating slip additives (see Fig. 2.22).
The need to protect sensitive electronic compo-
nents and computer boards from electrostatic
discharge during handling, shipping, and assembly
provided the driving force for development of
a different class of antistatic packaging materials.
These are sophisticated laminates with very thin
metalized films.
There are other additives used in plastics, but the
ones discussed above are the most common.
2.11 Summary
The basis of all films is polymers. But as discussed
in this chapter, the properties are complex and most
have some effect on permeation, diffusion, and
solubility. Most of this chapter did not go into the
chemical structures of all the polymers used in films,
containers, and membranes. The data of various
polymers/plastics are presented beginning from
Chapter 5 and the chemical structures of the poly-
mers are discussed in the appropriate sections.
References
1. Available from: http://en.wikipedia.org/wiki/
Dendronized_polymers
2. This is a file from the Wikimedia Commons
which is a freely licensed media file repository.
3. Stepto RFT. Dispersity in polymer science
(IUPAC Recommendations 2009). Pure Appl
Chem 2009;81:351e3.
37
4. Matsumoto T, Horie S, Ochiumi T. Effect of
molecular weight of ethyleneevinyl alcohol
copolymer on membrane properties. J Membr
Sci 1981;9:109e19.
5. Utracki LA. Polymer blends handbook, Vols.
1e2. Springer-Verlag; 2002. Available from:
http://www.knovel.com/knovel2/Toc.jsp?
BookID¼1117&VerticalID¼0.
6. Utracki LA. Commercial polymer blends.
Springer-Verlag; 1998. Available from: http://
www.knovel.com/knovel2/Toc.jsp?
BookID¼878&VerticalID¼0.
7. Utracki LA. Encyclopaedic dictionary of
commercial polymer blends. ChemTec
Publishing; 1994. Available from: http://www.
knovel.com/knovel2/Toc.jsp?
BookID¼285&VerticalID¼0.
8. Flick EW. Plastics additivesdan industrial
guide. 2nd ed. William Andrew Publish-
ing/Noyes; 1993. Available from: http://www.
knovel.com/knovel2/Toc.jsp?
BookID¼353&VerticalID¼0.
9. Pritchard G. Plastics additivesdan A-Z refer-
ence. Springer-Verlag; 1998. Available from:
http://www.knovel.com/knovel2/Toc.jsp?
BookID¼335&VerticalID¼0.
10. Choudalakis G, Gotsis A. Permeability of pol-
ymer/clay nanocomposites: A review. Eur
Polym J 2009;45:967e84.
11. Moggridge G. Barrier films using flakes and
reactive additives. Prog Org Coat 2003;46:
231e40.
12. Brubaker DW, Kammermeyer K. Flow of gases
through plastic membranes. Ind Eng Chem
1953;45:1148e52.